Antiperspirant composition containing dioxaluminin and dioxaluminane

ABSTRACT

An antiperspirant composition contains in a cosmetic carrier as an active compound a dioxaluminin or dioxaluminane derivative.

Bouillon et al,

ANTIPERSPIRANT COMPOSITION CONTAINING DIOXALUMININ AND DIOXALUMINANE Societe Anonyme dite: LOreal, Paris, France Filed: Mar. 25, 1974 Appl. No.: 454,732

Related [1.8. Application Data Division of Ser. No. 294,927, Oct. 4, 1972, Pat. No. 3,819,761.

Assignee:

Foreign Application Priority Data Dec. 16, 1971 Luxemburg 64463 11.8. C1. 424/46; 260/333; 424/DIG. 5;

[ Dec. 30, 1975 [51] Int. Cl. A61K 7/38 [58] Field of Search 424/47, 46, 68

[56] References Cited UNITED STATES PATENTS 3,444,226 5/1969 Schmank et a1. 424/47 3,819,671 6/1974 Bouillon et al. 424/47 X Primary ExaminerAlbert T. Meyers Assistant Examiner-Dale R. Ore

Attorney, Agent, or Firm-Cushman, Darby & Cushman 57 ABSTRACT An antiperspirant composition contains in a cosmetic carrier as an active compound a dioxaluminin or dioxaluminane derivative.

9 Claims, No Drawings This is a division of application Ser. No. 294,927, filed Oct. 4, 1972, now U.S. Pat. No. 3,819,761.

The present invention relates to a cosmetic antiperspirant composition, to certain compounds usefully employed in these compositions and to a process for preparing these compounds.

It is well known that perspiration which results from the secretion of sudoriferous glands causes moistness of the skin and that heretofore there has been proposed the use on the skin of a variety of materials to reduce perspiration.

These materials include, for instance, aluminum chlorhydroxide complex, known under the tradename CHLORHYDROL, sodium aluminum chlorhydroxy lactate complex, known under the tradename CHLO- RACEL, aluminum phenylsulfonate, aluminum allantoinate, aluminum dihydroxy allantoinate, aluminum isopropylate as well as various other organic aluminum compounds or complexes such as, for example, the complex of aluminum chlorhydroxide with propylene glycol known under the tradename REHYDROL.

Most of the compositions based on previously known antiperspirant compounds, while they may effectively inhibit or diminish perspiration, they do however exhibit'certain disadvantages which make their use in many cases quite difficult.

As will be appreciated, antiperspirant compositions are preferably used in the form of an aerosol spray and as such the antiperspirant compound must exhibit good solubility in alcohols, so as to provide good spraying or atomization characteristics.

Among the previously cited compounds, certain ones are insoluble in alcohol so that for an aerosol type composition they are generally useless. However, among those cited, some exhibit sufficiently good solubility characteristics in alcohol, notably ethanol, but

their antiperspirant activity is clearly less acceptable.

It has now been found that a certain class of heterocycle compounds based on aluminum provide excellent antiperspirant compositions, these compounds exhibiting the advantages of previously known compounds without, however, having their principal disadvantages.

Moreover, it has been observed that in most situations, the antiperspirant compositions of the present invention exhibit, relative to conventionally known antiperspirant compositions, surprisingly better antiperspirant characteristics.

More particularly, the present invention relates to an antiperspirant composition comprising in combination a cosmetic carrier and at least one active compound of the formula wherein R is selected from the group consisting of chlorine and -OSO R' wherein R is selected from the group consisting of alkyl having 1-4 carbon atoms, phenyl, p-chlorophenyl, tolyl and 2-oxo-10-bornanyl, and

2 Z represents a member selected from the group consisting of R2 CH2- wherein R is selected from the group consisting of a. COR wherein R is selected from the group consisting of (i) methyl and (ii) ethyl, in which case R is selected from the group consisting of methyl and ethyl and (iii) phenyl in which case R is selected from the group consisting of methyl, acetyl and COOR wherein R is alkyl containing 1-4 carbon atoms, COOR,, wherein R, has the meaning given above in which case R represents a member selected from the group consisting of methyl, -C E N and -COOR wherein R, has the meaning given above, and c. NO in which case R represents a member selected from the group consisting of bromine and alkyl radical containing l-3 carbon atoms, and

wherein R represents a member selected from the group consisting of d. methyl, in which case R is COOR and R represents -O-R wherein R in each instance represents alkyl having 1-4 carbon atoms, and e. hydrogen, in which case R is selected from the group consisting of iv. COR wherein R is selected from the group consisting of methyl, in which case R is selected from the group consisting of methyl and phenyl, and phenyl, in which case R is methyl;

v. -COOR in which case R is selected from the group consisting of methyl, phenyl and O-R wherein R has the same meaning given above; and

vi. -C E N in which case R represents O-R wherein R also has the above meaning.

Representative of the compounds usefully employed in the composition of the present invention are:

2-chloro-5,5-bis-(ethoxycarbonyl)-l ,3,2-dioxaluminane of the formula 2-chloro-5-cyano-5-ethoxycarbony1-1,3,2-dioxaluminane of the formula 2-ch1oro-5-cyano-4-ethoxy-1,3,2-dioxaluminin of the formula C H O 5 b enzoyl-2-chloro-5Fethoxycarbonyl-l ,3 ,2-dioxaluminane of the formula Al-Cl 2-chlo ro-5-ethoxycarbonyl-5-methyl-l,3,2-dioxaluminane of theformula c H 00 i CH3 Q/ The cosmetic compositions according to the present invention cancontain from 0.2 to 30%, and preferably, from 0.5 to 25% by weight of at least one active antiperspirant compound as defined above and can be provided in various forms, such as in the form of a lotion, a cream, a milk, a stick, a powder or in the form of an aerosol spray.

When th'e'com'positions according to the invention are provided in the form of a cream, the concentration of the active compound, in the cream base or carrier is preferablybetween 0.5 and 20 weight percent. The cream base or carrier is generally an oil-in-water emulsion comprising about 10 30 weight percent oil and 90 to 70 weight percent water. 4

Representative oils that can be employed to provide the oil phase of the emulsion include:

a. hydrocarbon oil such as paraffin oil, Purcellin oil,

perhydrosqualene and a solution of microcrystalline wax in oil;

b. animal or vegetable oil such as sweet almond oil, avocado oil, calophyllum oil, lanolin, castor oil, horse oil, pork oil and olive oil;

c. mineral oil having an initial distillation point, at atmospheric pressure, of about 250C and a final distillation point of about 410C; and

cl. saturated esters such as isopropyl palmitate, alkyl myristates wherein the alkyl moiety is selected from isopropyl, butyl and cetyl, hexadecyl stearate, ethyl palmitate, triglycerides of octanoic and decanoic acid and cetylricinoleate.

In the oil phase it is also possible to use silicone oils soluble in the other oils, such as dimethylpolysiloxane, methylphenylpolysiloxane and a siliconglycol polymer.

'To promote or improve the retention of oils, the oil phase can also contain a wax such as Carnauba wax, candellila wax, beeswax, microcrystalline wax and ozokerite, the amount of wax employed generally ranging from about 0 to 20 percent by weight based on the weight of the oil employed in said oil phase.

Fatty alcohols such as stearyl alcohol, cetyl alcohol, 2-octyl-1-dodecanol, oxyethylenated fatty alcohols, propylene glycol and the like, can also be employed in the production of creams in accordance with the present invention, said fatty alcohols usually being present in amounts of about 0.5 to 10 percent by weight of said composition.

When the compositions of the present invention are in the form of sticks, the concentration of active compound is preferably between 0.5 to 10 weight percent.

The antiperspirant composition made in stick form in accordance with the invention can be produced from molten wax in which is incorporated the active compound of this invention. Generally, the active compound is incorporated into the stick as an emulsion of a solution thereof in water, in lower alkanol such as ethanol or isopropanol or in an aqueous solution of a lower alkanol containing generally from 30 to by weight of said lower alkanol.

It has also been found advantageous, in the preparation of these antiperspirant sticks to introduce into the wax component about 0.5 to 10 weight percent based on the weight of the wax, an oil or fatty alcohol, as defined above.

The emulsifiers employed to produce the cream or stick of this invention can be those conventionally employed for these types of composition and particularly fatty amides such as coprah monoethanolamide, stearic diethanolamide and the like are usefully employed.

In the antiperspirant sticks of the present invention, the aqueous, alcoholic or hydroalcoholic solution of the active compound of the present invention represents about 10 to 60 weight percent of said stick.

When the composition according to the present invention is in powder form, the concentration of the active antiperspirant component is preferably between 5 and 25 weight percent of the total weight of the composition.

These compositions, in powder form, also can contain a conventional powder base and a binder. The powder base can be any conventional essentially nonhygroscopic powder commonly used in cosmetic or pharmaceutical products. illustrative of such materials are talc, magnesium carbonate, starches such as rice starch or cornstarch, clay such as kaolin or bentonite, powdered stearates such as lithium stearate, zinc stearate and magnesium stearate; and mixtures of the same. Typical binders include mineral oil, vegetable oil, lanolin, petroleum, fatty alcohols, isopropyl esters such as isopropyl myristate and isopropyl palmitate and the like.

Preferably, the cosmetic composition of the present invention is in the form of a sprayable aerosol which can be an alcohol-based spray, a dry spray or a powder spray.

in this particular embodiment, the concentration of the active antiperspirant compound is generally between 1 and 5 weight percent of the total weight of the aerosol composition.

The alcohol-based spray in aerosol form contains, in addition to the active antiperspirant compound, an anhydrous alcohol selected from the group consisting of ethanol and isopropanol and a liquified aerosol propellant under pressure such as a halogenated hydrocarbon including, for example, trichlorofluoromethane or 7 dichlorodifluoromethane and their mixtures. Obviously, other conventional aerosol propellants, inert with respect to the active compound of this invention can also be used.

In the case of a dry or powder spray, the composition contains in addition to the active compound and the liquified propellant as defined above, under pressure, a powder base and a binder also as defined above, the powder base being present in amounts of about 0.1 to 15 weight percent of the total aerosol composition and the binder, when present, being included in amounts of about 0.05 to weight percent by weight of said composition. Generally the propellant, in these aerosol compositions is present in amounts of about 66 to 75 weight percent of the total aerosol composition.

It is understood that whatever form of the composition of this invention is chosen, i.e. a cream, a stick, or an aerosol spray, any other conventional adjuvant generally used in these types of compositions, which is inert with respect to the active component can be employed. For instance, it has been found advantageous to include in the composition of the present invention a preservative such as methyl parahydroxybenzoate or propyl parahydroxybenzoate, as well as a perfume.

The present invention also relates to a compound of the formula Al-R wherein R is selected from the group consisting of chloro, -O-R" wherein R" is selected from the group consisting of methyl, ethyl, isopropyl and tertiary butyl, and --OSO R' wherein R is selected from the group consisting of alkyl having 1-4 carbon atoms, phenyl, pchlorophenyl, p-hydroxyphenyl, tolyl and 2-oxo-l0- bornanyl, and

Z is selected from the group consisting of in which R is selected from the group consisting of a. COR wherein R is selected from the group consisting of (i) methyl, (ii) ethyl, in which case R is methyl and (iii) phenyl, in which case R is selected from the group consisting of methyl, acetyl and -COOR wherein R is alkyl containing 14 carbon atoms;

b. COOR,, in which case R is selected from the group consisting of methyl, C E N and --COOR,, wherein R, has the meaning given above, and

c. NO.,,, in which case R is selected from the group consisting of bromine and alkyl containing l-3 carbon atoms; and

8 wherein R is selected from the group consisting of d. methyl, in which case R represents COOR and R represents O-R wherein R represents alkyl having l-4 carbon atoms; and

5 e. hydrogen, in which case R is selected from the group consisting of (iv) COR wherein R is selected from the group consisting of methyl, in which case R is selected from the group consisting l 0 of methyl and phenyl, and phenyl, in which case R 3O 5-acetyl-2-chloro-5-methy1-l ,3,2-dioxaluminane;

5-benzoyl-2-chloro-5-methyl-1,3,2-dioxaluminane; 2-chloro-5-cyano-4-ethoxy-1,3 ,2-dioxaluminin; 5-benzoyl-2-chloro-5 -ethoxycarbonyl-l ,3 ,2-dioxaluminane;

2-chloro-5-ethoxycarbonyl-5-methyl-l ,3 ,2-dioxaluminane;

2-chloro-5-ethoxycarbonyl-4-phenyl-l ,3 ,2-dioxaluminin;

5-acetyl-5-benZoyl-2-chloro-l ,3 ,2-dioxaluminane;

5-acetyl-2-chloro-4-phenyl-l ,3 ,Z-dioxaluminin;

5-benzoyl-2-chloro-4-methyl-l ,3,2-dioxaluminin;

2-chloro-4-ethoxy-5-ethoxycarbonyl-6-methyl-1,3 ,2- dioxaluminin;

2-isopropoxy-5-bromo-5-nitro-l ,3,2-dioxaluminane of the formula 0 N -'-''O CH 2 3 AlO-CH 5 Br' o cn 2-isopropoxy-5-ethoxycarbonyl4-ethoxy-l ,3,2-dioxaluminin of the formula 0 00 11 0 CH 3 C2H5 o A O Al o CH 5-benzoyl-2-isopropoxy-4-methyl-l ,3 ,2-dioxalumi nin of the formula CH O 3 ll 0 ca 3 Al-O-CH o ca 9 10 5-acetyl-2-isopropoxy 4-phenyl-l ,3 ,2-dioxaluminin of the formula H C H O- CH 2 5 :O Al-O-CH 3 CH CH CH -c- Al-O-CH 3 3 5 h 3 0/ \CH -et oxycarbony]-2-1sopropoxy-4-phenyl-l,3,2-diox- 0 3 aluminin of the formula 4-ethoxy-5-ethoxycarbonyl-2-isopr opoxy-6-methyl- 0 CH 1,3,2-dioxaluminin of the formula c H 3 and 0 CH O I C H O o CH 2,4-diethoxy-S-ethoxycarbonyl-l ,3 ,2-dioxaluminin 2 3 5 of the formula |l 0 CH 1 00 H CH 2 O C H O-C Al-OC H 5-cyano-5-ethoxycarbonyl-2-isopropoxy-l,3,2-diox- O aluminane of the formula o The present invention is also related to a process for preparing the active compound of formula (IV). c H 0.0 Q CH These active compounds in which Z represents a 2 5 X Al-o-cH 3 5 radical of formula (II) are'prepared by starting with a N 0/ 30 B-glycol (1) according to the following reaction scheme:

R /CH OH R /CH O\ c\ (R"O Al c\ /Al-O-R" a R/ 0 R CH OH 2 Ch -O R /CH -O R CH -O\ /C\ Al-O-SO R' Al-Cl R GH -O R CH 5-cyano-4-ethoxy-2-isopropoxy-l ,3,2-dioxaluminin wherein R" CH C l-l CH(CH or C(CH of the formula Generally speaking, the active compound of this invention can be produced by reacting an anhydrous CZHSO solvent medium and equimolar amounts of B-glycol (l with an aluminum alcoholate. N G A1-O-C /CH3 The B-glycols (l) employed can be prepared by ac- 3 tion of formaldehyde on a compound possessing at least one electro-attractive function, such as a car- 5-ethoxycarbonyl-2-isopropoxy-5-methyl-1,3,2-dioxbony], cyano or nitro group. A certain number of these aluminane of the formula B-glycols are described in the literature:

Ardis et coll. J.A.C.S.,

Morgan, Chem lnd 1938,

R =R CEN RFCOCH and R =CH or coca-1,

R =NO and R alkyl Morgan, J.Chem.Soc., I932 p.2267

Vanderbilt, lnd.Eng.Chem., I940 32, 34.

Walker, Formaldehyde, Reinhold, 1964, p.291, CA 68 P 60535/8 Further, it is apparent that, when R and R are both 15 electro-attractive, as is the case of active methylene compounds, it is most often unnecessary to proceed to isolate and to purify the B-glycol. In effect, the transformation of the active methylene compound to the B- glycol of type (1) is effected in a practically quantitative manner and the crude product of the reaction, extracted by an appropriate solvent, is most often suitable for the preparation of aluminum derivatives (2), (3) and (4). This process is particularly advantageous for it limits to a minimum the number of operating 25 steps to be taken.

C R CH OH CH OH the boiling point of the solvent. Representative useful anhydrous solvents for this reaction, include an alcohol, such as ethyl, methyl, isopropyl and tertio-butyl alcohol, an aromatic hydrocarbon such as benzene and toluene, a chlorinated hydrocarbon such as chloroform, esters and ethers.

For the preparation of compounds of formula (3) and (4), it is not necessary to isolate the compound of formula (2). In effect, the solutions of compounds (2) in the anhydrous solvent medium can be directly reacted either with gaseous hydrochloricacid to produce compound (3) or with sulfonic acid in solution in an anhydrous solvent to produce the compound (4).

Compounds (3) and (4) can be easily isolated by evaporation of the reaction solvents.

The preparation of compounds of formula (IV) in which Z represents a radical of formula (Ill) and R represents hydrogen, is realized according to scheme B, by reacting initially a compound of formula (5) in the presence of an aluminum alcoholate under the same conditions given above for the preparation of compounds of formula (2). One obtains thus the compound of formula (6) which by simple heating is transformed into a compound of formula (7) with release of formol.

SCHEME B o R i CH 5- 2 (R"O) Al c Al-OR" R6 ca -o D" H01 re heat The compounds of formula 7 can generally be isolated or transformed directly into compounds of formula 8 by reaction with hydrochloric acid or into compounds of formula 9 by reaction with sulfonic acid.

513 The preparation of compounds of formula (IV) in which the radical Z represents the radical of formula (III) and R represents 'a methyl radical is effected according to scheme C by reacting the compounds of formula (10) in the presence of aluminum alcoholate under the same conditions as those described above. There is thus obtained the compound of formula (11) which can easily be isolated or transformed directly into compounds of formula (12) by reaction with hydrochloric acid or into compounds of formula (13) by reaction with a sulfonic acid.

wherein R and R are as above defined and 2.2 to 3.0 moles of a 30% aqueous formaldehyde solution are mixed and cooled to a temperature of -20 to lC. There is then added to this solution 2 to 8 g of potassium carbonate, dissolved in a minimum amount of water. The resulting mixture is stirred for a period of about 15 to 120 minutes while maintaining the temperature between 0 and lC. The solution is then saturated with ammonium sulfate and extracted with an appropriate solvent such as ethyl acetate or ether. After drying in the presence of anhydrous magnesium It must be remarked that the preparation of compounds of formula (IV), in which R represents chlorine, by the reaction of hydrochloric acid with compounds of formula (IV) wherein R represents alkoxy,

is often incomplete because of a deficiency of chlorine with respect to aluminum. However, the rate of conversion is nevertheless always greater than or at least equal to 80%.

There will now be given by way of illustration and without any limiting character, several examples of the preparation of the active compounds of the present invention and some representative examples of the preparation of antiperspirant compositions of the invention using these active compounds. It will be noted that these active compounds' are characterized by having substituted atposition 5 of the dioxaluminin or dioxaluminane at least one electro-attractive group such asan ester, a ketone, at nitrile or a n itro group. These electro-atti'active groups thus confer to the compositions of the invention some excellent properties.

. GENERAL METHOD QF PREPARING BETA-GLYCOLS OF FORMULAE (I) AND (5) One mole of an active methylene product of the formula:

sulfate, the extracted solution can be utilized directly for reaction with an aluminum alcoholate according to schemes A or B.

EXAMPLES OF PREPARATION EXAMPLE 1 Preparation of 2-chloro-5 ,5-bis-(ethoxycarbonyl)- l ,3,2-dioxaluminane.

Method A There is heated to reflux, for a period of 2 hours with continuous stirring, a mixture comprising a solution of 20.4 g of aluminum isopropylate in ml of benzene and a solution of 22 g of bis-(hydroxymethyl) ethyl malonate in 160 ml of methanol. After cooling this mixture to ambient temperature, there is added to the gel thus obtained 33.3 ml of a solution of 3N dry hydrochloric acid in isopropanol. The resulting reaction mixture is then continued to be stirred for a period of one hour.

After evaporating the solvent under reduced pressure there is thus obtained a colorless crystalline appearing product exhibiting yellowish glints. This product is obtained with b mole of isopropanol of solvation.

Calculated Found Yield (g) 31.05 29.76 Al (meq/g) 3.22 3.28 Cl (meq/g) 3.22 2.97

Method B There is stirred for a period of 3 hours at ambient temperature a mixture of 8.8 g of 2,2-bis-(hydroxymethyl) ethyl malonate and 6.5 g of aluminum ethylate in 150 ml ethanol. To this mixture there are then added 8.5 ml ofa 4.75 N dry hydrochloric acid solution in ethanol and the resulting mixture is heated at 55C for a period of 30 minutes. The resulting solution is evaporated to dryness under reduced pressure at a temperature lower than 50C, thereby producing a colorless solid containing V2 mole of ethanol of solva tlon.

Calculated Found Yield (g) 12.15 12.35

Al (meq/g) 3.3 3.17

Cl (mq/g) 3.3 2.81

EXAMPLE 2 Calculated Found Yield (g) 34 34.7 A] (meq/g) 2.94 2.90

EXAMPLE 3 Preparation of Z-para-toluene sulfonyloxy-5,5-bis- (ethoxycarbonyl)-1,3 ,2-dioxaluminane There is heated for a period of 2 hours at 50C a mixture comprising a solution of 22 g of bis-(hydroxymethyl) ethyl malonate in 100 ml of chloroform and a solution of 20.4 g of aluminum isopropylate in. 100 ml of chloroform.

After cooling, there is then added a solution of 17.2 g of anhydrous para-toluene sulfonic acid in 300 ml of benzene and the reaction mixture is stirred for a period of 1 hour. Subsequently, the reaction mixture is evaporated to dryness under reduced pressure, thereby producing a yellowish white solid product. This product is obtained with V2 mole of isopropanol of solvation.

EXAMPLE 4 Preparation of 2-isopropoxy-5-ethoxycarbonyl-4- ethoxyl ,3 ,2-dioxaluminin.

There is heated to reflux for a period of 2 hours with continuous stirring a mixture comprising a solution of 22 g of bis-(hydroxymethyl) ethyl malonate in 200 ml of methanol and a solution of 20.4 g of aluminum iso- O propylate in 200 ml of benzene. The resulting mixture is then evaporated to dryness under reduced pressure at a temperature of about C, thus yielding a colorless crystalline appearing solid.

Calculated Found Yield (g) 27.4 26.8 Al (meq/g) 3.64 3.64

EXAMPLE 5 Preparation of 2-chloro-5-ethoxycarbonyl-4-ethoxy- 1,3 ,2-dioxaluminin.

To a suspension of 27.4 g of 2-isopropoxy-5-ethoxycarbonyl-4-ethoxy-l,3,2-dioxaluminin in ml of methanol, there are added 50 ml of a solution of 2N dry hydrochloric acid in isopropanol. The resulting mixture is agitated for a period of 3 hours and then evaporated to dryness under reduced pressure, thereby yielding a colorless crystalline appearing product exhibiting yellowish glints. This product is obtained with A mole isopropanol of solvation.

Calculated Found Yield (g) 28.05 27.3 Al (meq/g) 3.56 3.52 C1 (meq/g) 3.56 3.10

EXAMPLE 6 Preparation of 2-isopropoxy-5-bromo-5-nitro-1,3,2- dioxaluminane.

There is heated to reflux for a period of 2 hours a mixture comprising a solution of 20.4 g of aluminum isopropylate in 100 ml of benzene and a solution of 20 g of 2-bromo-2-nitro-1,3-propanediol in 100 ml of methanol.

After evaporation of the solvents under reduced pressure, there is thus obtained a white powder.

Calculated Found Yield (g) 28.4 28.4 Al (meq/g) 3.52 3.38

EXAMPLE 7 Preparation of 2-chloro-5-bromo-5-nitro-1,3,2-dioxaluminane.

17 There is heated to reflux for a period of 2 hours with continuous agitation a mixture comprising a solution of 10.2 g of aluminum isopropylate in 50 ml of benzene and a solution of g of 2-bromo-2-nitro-1,3-

Calculated Found Yield (g) 14.52 14.98

Al (meq/g) 3.44 3.35

CI (meq/g) 3.44 3.17

EXAMPLE 8 Preparation of 2-chloro-5-ethoxycarbonyl-4-methyl- 1,3,2-dioxaluminin.

There is stirred for a period of 2 hours at ambient temperature a mixture of a solution of 190 g of 2,2-bis- (hydroxymethyl) ethyl acetylacetate in 1 liter of methanol and a solution of 204 g of aluminum isopropylate in a liter of benzene. After permitting the resulting mixture to stand overnight there are then added 333.3 ml of a solution of 3 N dry hydrochloric acid in isopropanol and the resulting reaction mixture is then stirred for a period of 2 hours.

At the end of this time the solvents are evaporated under reduced pressure, thus yielding a yellow crystalline appearing product. This product is obtained with 54 mole of isopropanol of solvation.

There is stirred for a period of 5 hours at ambient temperature a mixture comprising a solution of 8 g of bis-(hydroxymethyl) acetylacetone in 80 ml of methanol and a solution of 10.2 g of aluminum isopropylate in 80 ml of benzene.

At the end of this time there are then added to this mixture 25 ml of a solution of 2 N dry hydrochloric acid in isopropanol and the resulting mixture is left to stand overnightI After evaporation to dryness of the reaction mixture there is thus obtained a light beige powder. This product is obtained with 4 mole of isopropanol of solvation.

18 EXAMPLE 10 Preparation of 2-chloro-5-cyano-5-ethoxycarbonyl- 1,3,2-dioxaluminane.

There is stirred for a period of 2 hours at ambient temperature a mixture comprising a solution of 204 g of aluminum isopropylate in a liter of benzene and a solution of 173 g of bis-(hydroxymethyl) ethyl cyanacetate in a liter of methanol. There are added to this mixture 350 ml of a solution of 2 N dry hydrochloric acid in isopropanol. Stirring of the reaction mixture is continued for one hour. At the end of this time, the product passes into solution.

After evaporation of the solvents, under reduced pressure, there is obtained a colorless crystalline appearing product. This product is obtained with /2 mole of isopropanol of solvation.

Calculated Found Yield (g) 263.5 268 Al (meq/g) 3.79 370 C1 (meq/g) 3.79 3.12

EXAMPLE ll Calculated Found Dioxaluminane Dioxaluminin Yield (g) 51.4 45.4 49.3 A1 meq/g) 3.86 4.40 4.06

There is thus obtained a mixture which includes about 65% dioxaluminane and 35% dioxaluminin. Conversion to Dioxaluminane.

30 g of the mixture obtained above are heated to C under a pressure of 20 mm of mercury for 2 hours in a rotating evaporator.

Calculated Found Yield (g) 27.72 27.18

A1 (meq/g) 4.40 4.39

EX AM PLE l 2 2-chloro-5-cyano-4-ethoxy-1,3 ,2-dioxaluminin.

19 To a suspension of 10 g of 2-isopropoxy-5-cyano-4- ethoxy-l ,3,2-dixaluminin in 100 ml of methanol there are added 25.2 ml of a solution of 1.74 N dry HCl in isopropanol and the resulting reaction mixture is stirred 20 There is stirred for a period of 2 hours at ambient temperature a mixture comprising a solution of 7.4 g of 2,2-bis-(hydroxymethyl)-3-oxo-3-phenyl ethyl propanoate in 29 g of ethyl acetate (as described in for a period of 1 hour. After evaporation to dryness 5 Example 14) and a solution of 5.98 g of aluminum under reduced pressure and drying at 80C the is isopropylate in 20 ml of chloroform. The mixture is ob a Sol yellow product ncl g 5% m of evaporated to dryness at reduced pressure at a temperlsopropanol of Solvationi ature lower than or equal to 40C, thus yielding a white powder.

Calculated Found Yield (g) 1015 1052 Calculated Found A (meq/g) 4.27 4.08

Yield (g) 8.96 9.2 Ci (meq/g) 4.27 4.01 15 Al (meq/g) 3'26 319 EXAMPLE l3 EXAMPLE 16 5-acetyl-2-chloro-5-methyl-l ,3,2-dioxaluminane. There is heated to reflux for a period of 1% hours a 20 pro-5-ethoxycarbonybLphenyl'132-dloX mixture of 28.8 g of 3,3-bis-(hydroxymethyl)-2-butaa none in l00 ml of chloroform and a solution of 36.7 g METHOD A of aluminum isopropylate in 100 ml of chloroform. After cooling, there are added 85.7 ml of a solution of There ml of a solution. of N dry 2.1 N dry HCl in isopropanol. The resulting reaction hydrochlonc ethanol to a Solution of g of mixture is stirred for a period of one hour. After evapo- 5ethfnfycfubonyl-2'lsopropoxy-4'phenyl'l 32'dl0X: ration to dryness there is thus produced an Orange aluminin in 15 ml of ethanol. The resultmg reaction powder The product retains 1k mole of isopropanol of mixture 1s stirred for a period of 1 hour and 1t 1s then Solvatiom evaporated to dryness under reduced pressure at a temperature of 55 to 60C. There is thus recovered a white powder. This product retains '12 mole of isopropa- Calculated Found 0 Yield (g) 40 40 Al (meq/g) 4.5 4.35 CI (meq/g) 4.5 4.22 Calculated Found Yield (g) 6.12 5.9 Al (meq/g) 3.20 3.23 Cl (meq/g) 3.20 2.93 EXAMPLE l4 5 -benzoyl-2-chloro-5-ethoxycarbonyll ,3 ,2-dioxaluminan e. l METHOD B There is stirred for a period of 2 hours at ambient temperature a mixture comprising a solution of 14.8 g Thfere mlxed and surfed for a Perlod of 1 hour a of 2,2-bis-(hydroxymethyl)-3-oxo-3-phenyl ethyl pro- 50mm)" of g of '9 y y y pionate in 57 g of ethyl acetate (this solution is ob- P Y Y propanoate m 40 ml of f y acetate tained by extraction of the reaction product of ethyl desclilbed Example and a Solutlon of g of benzoylacetate and formaldehyde according to the alummum p py 15 ml of chloroformgeneral method described above for the preparation of There added of 9 of N B g]ycO1S) and a Solution f 1 94 g f aluminum i dry HCl 1n isopropanol followed by stirring the reaction propylate in 25 ml of chloroform. There are then added mlxture for a Pi?rlocl of 4 hours- Thereafter, the reac- 2 4 1 f a solution f4 72 N dry Hcl in ethanol and tion mixture is evaporated to dryness under reduced the stirring is maintained for a period of 1 hour. After Pressure at F PF of T colorless P evaporation to dryness under reduced pressure at a def thus Obtamed "19111965 1/5 mole p p temperature 5. 40, there is thus obtained a colorless powder. This powder contains a 72 mole of isopropanol of 8 01V ati on Calculated Found Yield (g) 29.5 29.6 Al (meq/g) 3.20 3.35 Calculated Found Cl (mm/g) Yield (g) 20.1 20.5 Al (meq/g) 2.92 2.88 01 (meq/g) 2.92 2.87 METHOD C 10 g of 2-chloro-5-ethoxycarbonyl-5-benzoyl-1,3,2- EXAMPLE 15 5 dioxaluminarie are heated for a period of] hour at a 5 -ethoxycarbonyl-2-isopropoxy-4-phenyl-l ,3 ,2-dioxaluminin.

temperature of C under reduced pressure. There is thus obtained 9.2 g of a white powder (theoretical weight 9.13 g).

-benzoyl-2-isopropoxy-4-methyl-1 ,3 ,2-dioxaluminin and(or) 5 acetyl-2-isopropoxy-4-phenyl-l,3,2- dioxaluminin.

There is cooled to C, a mixture of 12.98 g of benzoylacetone, 24 g of a 30% aqueous solution of formaldehyde and ml of dioxan. Then there is added a solution of 0.4 g of potassium carbonate in 1 ml of water. The resulting reaction mixture is stirred for 1 hour while maintaining the same at a temperature between 0 to 5C. The resulting solution is saturated with 8 g of ammonium sulfate and twice extracted with ethyl acetate. The solution resulting from the extraction is dried in the presence of anhydrous magnesium sulfate, thus yielding 74.6 g of a 25.8% solution of 2,2-bis-(hydroxymethyl)-l-phenyl 1,3-butanedione in ethyl acetate.

30.1 g of this solution are treated with stirring for 4 days at ambient temperature with a solution of 7.15 g of aluminum isopropylate in 15 ml of chloroform. After evaporation to dryness under reduced pressure at a temperature of 50C, .a yellow powder is obtained.

Calculated Found Yield (g) 9.66 9.52

Al (meq/g) 3.62 3.67

EXAMPLE 18 5-benzoyl-2-chloro-4-methyl-l,3,2-dioxaluminin and(or) 5-acetyl-2-chloro-4-phenyl-1,3 ,2-dioxaluminin.

4.8 g of the product described in Example 17 are suspended in 10 ml of ethanol. To the resulting suspension there are added 3.7 ml of a solution of 4.7 N dry HCl in ethanol. The mixture is stirred for 30 minutes and then evaporated to dryness under reduced pressure at a temperature of 60C. There is thus obtained a yellow powder which includes 12 mole of isopropanol of solvation.

, Calculated Found Yield (g) 4.92 5.09

Al (meq/g) 3.54 3.46

Cl (meq/g) 3.54 2.97

EXAMPLE l9 22 ture lower than or equal to 40C, thus yielding a yellow powder. The product retains 7% mole of isopropanol.

ophenone.

There is heated for a period of 15 hours in a boiling water bath a mixture of 26.8 g of propiophenone, 45 g of 40% aqueous solution of formaldehyde, 40 ml of ethanol and 1 g of potassium carbonate. The reaction mixture is poured into 250 ml water and extracted with methylene chloride. The organic extract is washed with water'and dried on anhydrous magnesium sulfate. After evaporation of the solvent there are recovered 32.7 g of oil which is then purified by chromatography in a column of Mallinchkrodt mesh silica. There is thus obtained 11.8 g of a product which crystallizes in isopropyl ether in the form of white needles, melting at 78C.

nane.

There is heated for a period of 1 hour in a boiling 5-benzoyl-2-chloro-5-methyl-1 ,3 ,2-dioxalumiwater bath a mixture comprising a solution of 0.73 g of [3,B-bis-(hydroxymethyl) propiophenone in 10 m1 of ethyl acetate and a solution of 0.77 g of aluminum isopropylate in 5 ml of chloroform. After cooling, there is added a solution of 0.8 ml of 4.75 N dry HCl in ethanol and the resulting mixture is left to stand for 30 minutes. The mixture is then evaporated to dryness under reduced pressure thus yielding a yellowish powder which includes 7% mole of isopropanol of solvation.

Calculated Found Yield (g) 1.07 1.03

Al (meq/g) 3.52 3.52

CI (meq/g) 3.52 3.32

EXAMPLE 21 Calculated Found Yield (g) 4.45 4.20 Al (meq/g) 4.06 4.23

EXAMPLE 22 2-chloro-5-ethoxycarbonyl-5-methyl-l ,3,2-dioxaluminane.

There is heated to reflux for a period of 1 hour a mixture comprising a solution of 6.4 g of 2,2-bis-(hydroxymethyl) ethyl propionate in 15 ml of ethyl acetate and a solution of 8.1 g of aluminum isopropylate in 25 ml of chloroform. After cooling there are added 8.4 ml

of a solution of 4.75 N dry HCl in ethanol. The result- 1 ing reaction mixture is stirred for 1 hour. After evaporation to dryness under reduced pressure there is obtained a solid colorless product containing a ,6 mole of isopropanol of solvation.

Calculated Found Yield (g) 10 Al (meq/g) 3.95 4.02 C1 (meq/g) 3.95 3.27

EXAMPLE 23 Calculated Found Yield (g) 16.7 16.8 Al (meq/g) 3.47 3.45

EXAMPLE 24 2-chloro-4-ethoxy-5-ethoxycarb0nyl-6-methyl 1,3,2- dioxaluminin.

A solution of 14.6 g of the product obtained in Example 23, in 50 ml of ethanol, is reacted with stirring for 30 minutes with 10.7 ml ofa solution of 4.75 N dry HCl in ethanol. The resulting solution is concentrated to dryness under reduced pressure at a temperature of 70C, thus yielding a beige colored solid retaining a 4 mole isopropanol.

Calculated Found Yield (g) 14.7 14.0 Al (meq/g) 3.4 3.53 Cl (meq/g) 3.4 2.97

EXAMPLE 25 2,4-diethoxy-5-ethoxycarbonyl-1,3 ,2-dioxaluminin.

There is heated to the boil for a period of 1 hour a mixture of 4.4 g of 2,2-bis-(hydroxymethyl) ethyl malonate (see Example 23) and 3.24 g of aluminum ethylate in 70 ml of ethanol.

24 After evaporation to dryness under reduced pressure there is obtained a colorless powder.

Calculated Found Yield (g) 5.20 5.21 Al (meq/g) 3.85 3.86

EXAMPLES OF COMPOSlTlON EXAMPLE 26 An antiperspirant cream according to the invention is prepared by mixing the following:

Stearyl alcohol oxyethylenated with 15 moles ethylene oxide 12 g Spermaceti wax 4 g lsopropyl myristate 3 g Silicone oil (density at 25C=1.051.08;

refractory index, 1.4851.495) 0.5 g Methyl para-hydroxybenzoate 0.1 g Propyl para-hydroxybenzoate 0.1 g Propylene glycol 2 g 2-chl0ro-5,S-bis-(ethoxycarbonyl) 1,3,2-dioxaluminane 2 g Perfume 0.5 g Water, q.s.p. 100 g EXAMPLE 27 An antiperspirant stick according to the invention is prepared by mixing the following ingredients:

Stearyl alcohol 10 g Microcrystalline wax 4 g Paraffin 10 g Coprah monoethanolamide 10 g Stearic diethanolamide 10 g 2-octyl-l-dodecanol 10 g Propylene glycol 20 g Ethyl alcohol 20 g Perfume 1 g 2-chloro-5,S-bis-(ethoxycarbonyl) 1,3,2-dioxaluminane 5 g EXAMPLE 28 An antiperspirant stick according to the invention is prepared by mixing the following ingredients:

Stearic diethanolamide Mixture consisting of 30% cetyl alcohol and stearyl alcohol, oxyethylenated with 13 moles of ethylene oxide per mole of alcohol of themixture Water Microcrystalline wax Perhydrosqualene Beeswax Ethyl alcohol 2-chlor0-4-ethoxy-5-ethoxycarbonyl 1.3,2-dioxaluminin Perfume EXAMPLE 29 An alcohol-based spray according to the invention is prepared by mixing the following ingredients:

Hexachlorophene 0.1 g 2-chloro-4-methyl-S-ethoxycarbonyl 1,3,2-dioxaluminin 5.2 g Perfume l g yl-l ,3 ,2-dioxaluminane -continued Ethyl alcohol 93 ,7 g

50 g of this mixture are packaged in an aerosol container together with 50 g of dichlorodifluoromethane.

There is obtained an equally excellent alcohol-based spray by replacing the 2-chloro-4-methyl-5-ethoxycarbonyl-l ,3,2-dioxaluminin by the following compounds:

5 ,5 -bis-( ethoxycarbonyl )-2-p-toluenesulfonyloxy- 1,2,3-dioxaluminane; 5-benzoyl-2-chloro-4-methyl- 1,3,2-dioxaluminin; and 2-chloro-4-ethoxy-5-ethoxycarbonyl-6-methyl-l ,3 ,2-dioxaluminin.

EXAMPLE 30 An alcohol-based spray according to the invention is prepared by mixing the following components:

Compound of the formula:

C l OH 2-chloro-5-acetyl-4-methyl-1,3,2-

dioxaluminin g Perfume l g Lanolin oxyethylenated with 16 moles of ethylene oxide 0.5 g Absolute ethyl alcohol, q.s.p. 100 g EXAMPLE 31 A dry antiperspirant spray according to the invention is prepared by mixing the following components:

2-chloro-5 -cyano-5-nitrol .3 ,2-

dioxaluminane 35 g Colloidal silica 3 2 Perfume 7- g lsopropyl palmitate, q.s.p. 100 g g of this mixture are then packaged in an aerosol container together with 45 g of trichlorofluoromethane and 45 g of dichlorodifluoromethane.

EXAMPLE 32 A dry antiperspirant spray according to the invention is prepared by mixing the following components:

5-acetyl-2-chloro-4-phenyl-l ,3 ,2-

dioxaluminin 35 g Colloidal silica 3 g Perfume 7 g Triglyceride fatty acid of C -C q.s.p. l00 g 10 g of this mixture are then packaged in an aerosol container, together with 45 g of trichloro'fluoromethane and 45 g of dichlorodifluoromethane.

EXAMPLE 33 A dry spray according to the invention is prepared by mixing the following components:

2-chloro-5-ethoxycarbonyl-4-phenyll,3,2-dioxaluminin 3.5 g Hexachlorophene 0.1 g Perfume 0.2 g Starch ester 0.3 g Silicone oil 1.2 g Trichloromonofluoromethane 47.35 g Dichlorodifluoromethane 47.35 g

EXAMPLE 34 A dry talc-based spray according to the invention is prepared by mixing the following components:

Sorbitan trioleate (viscosity at 25C=25O cps, HLB 1.8 (hydrophilic lypophilic balance)) lsopropyl myristate Deodorized kerosene Polyethylene glycol (M.W. 400) Colloidal silica Microtalc (5 microns) Perfume 2-chloro-5-bromo-5 -nitro-l ,3 ,2-

dioxaluminane 10 g of this mixture are then packaged in an aerosol container together with 45 g of trichloromonofluoromethane and 45 g of dichlorodifluoromethane,

An equally excellent spray is obtained by replacing the 2-chloro-5-bromo-5-nitro-l ,3 ,2-dioxaluminane with 2-methanesulfonyloxy-5,5'-bis-(ethoxycarbonyl)- l ,3 ,2-dioxaluminane.

EXAMPLE 35 A deodorant talc in the form of a spray is prepared by mixing the following components:

Sorbitan trioleate lsopropyl myristate 6 Deodorized kerosene Polyethylene glycol (M.W. 400) Colloidal silica Microtalc (5 microns) 2 Perfume 2-chloro-5 -cyano-4-ethoxy-l .3 .2-

dioxaluminin 10 g of this mixture are then packaged in an aerosol container together with 45 g of trichloromonofluoromethane and 45 g of dichlorodifluoromethane.

EXAMPLE 36 A composition in the form of a compressed powder according to the invention is prepared by mixing the following ingredients:

Talc g Lanolin 2.5 g Vaseline oil 2 g Perfume 0.5 g 2-chloro-S-ethoxycarbonyl-S-methyll,3,2-dioxaluminane 25 g What is claimed is:

1. An antiperspirant cosmetic composition comprising in a solvent selected from the group consisting of water, a lower alkanol and an aqueous solution of said 27 lower alkanol, 02-30 percent by weight of an active compound having the formula Z Al-R wherein R is selected from the group consisting of chloro, I

O-R" wherein R" is selected from the group consisting of methyl, ethyl, isopropyl and tertiary butyl and OSO R' wherein R is selected from the group consisting of alkyl having l4 carbon atoms, phenyl, p-chlorophenyl, hydroxyphenyl, tolyl and 2-oxo-lO-bornanyl, and

Z represents a member selected from the group consisting of wherein R is selectedfrom the group consisting of a. COR wherein R is selected from the group consisting of (i) methyl, (ii) ethyl, in which cases R is methyl, and (iii) phenyl in which case R is selected from the group consisting of methyl,

' 'acetyl and COOR, wherein R is alkyl containing -l4 carbon atoms,

b. "''COOR wherein R has the meaning given above in which case R represents a member selected from-the group consisting of methyl, C"= N and 'COOR wherein R, has the meaning given above,

0. N0 in which case R represents a member selected from the group consisting of bromine and alkyl containing l-3 carbon atoms; and

wherein 1 R represents a member selected from the group consisting of d. methyl, in which case R is COOR and R repre- 'sents O'-R wherein R represents alkyl having l-4 carbon atoms, and i e. hydrogen, in which case R is selected from the 28 2. The composition of claim 1 wherein said active compound is selected from the group consisting of 2-chloro-5 ,5-bis-(ethoxycarbonyl)-l ,3,2-dioxaluminane,

2ch1oro-5-cyano-5-ethoxycarbonyl-l,3 ,Z-dioxaluminane,

2-chloro-5-bromo-5-nitrol ,3,2-dioxaluminane,

2-chloro-5-ethoxycarbonyl-4-ethoxy-1,3,2-dioxaluminin,

2-chloro-5-ethoxycarbonyl-4-methyl-l ,3 ,Z-dioxaluminin,

2-chloro-5-acetyl-4-methyl-l ,3 ,2,-dioxaluminin,

Z-methanesulfonyloxy-S ,5-bis-(ethoxycarbonyl)-l 3,

2-dioxaluminane, 5 ,5 -bis-( ethoxycarbonyl )-2-p-toluene sulfonyloxy- 3. The composition of claim 1 wherein said active compound is present in amounts between 05-25 percent by weight of said composition.

4. An antiperspirant cosmetic powder composition comprising in a carrier selected from the group consisting of talc, magnesium carbonate, rice starch, cornstarch, kaolin, bentonite, lithium stearate, zinc stearate, magnesium stearate and mixtures thereof, 02-30 percent by weight of an active compound having the formula z Al-R wherein R is selected from the group consisting of chloro, O-R" wherein R" is selected from the group consisting of methyl, ethyl, isopropyl and tertiary butyl and SO R wherein R is selected from the. group consisting of alkyl having l-4 carbon atoms, phenyl, p-chlorophenyl, hydroxyphenyl, tolyl and 2-oxo-l O-bornanyl, and Z represents a member selected from the group consisting of R CH,-

wherein R is selected from the group consisting of a. COR wherein R is selected from the group consisting of (i) methyl, (ii) ethyl, in which cases R is methyl, and (iii) phenyl, in which case R is selected from the group consisting of methyl, acetyl and COOR wherein R is alkyl containing l-4 carbon atoms,

b. -COOR wherein R, has the meaning given above in which case R represents a member selected from the groupconsisting of methyl, C= N and COOR wherein R has the meaning given above,

0. -NO in which case R represents a member selected from the group consisting of bromine and alkyl containing 1-3 carbon atoms; and

wherein R represents a member selected from the group consisting of d. methyl, in which case R is COOR and R represents O-R wherein R represents alkyl having l-4 carbon atoms, and e. hydrogen, in which case R is selected from the group consisting of iv. -COR wherein R is selected from the group consisting of methyl, in which case R is selected from the group consisting of methyl and phenyl, and phenyl, in which case R is methyl; v. --COOR in which case R is selected from the group consisting of methyl, phenyl and O-R wherein R has the meaning given above; and vi. --C N in which case R represents O-R wherein R has the meaning given above.

5. The antiperspirant cosmetic powder composition of claim 4 wherein said active compound is present in an amount between 5-25 percent by weight of said composition.

6. The antiperspirant cosmetic powder composition of claim 4 which also contains a liquified aerosol propellant selected from the group consisting of trichlorofluoromethane, dichlorodifluoromethane and mixtures thereof, said composition being packaged under pressure in an aerosol container.

7. An antiperspirant cosmetic aerosol composition packaged under pressure in an aerosol container comprising in a liquified aerosol propellant selected from the group consisting of trichlorofluoromethane, dichlorodifluoromethane and mixtures thereof, 02-30 percent by weight of an active compound of the formula Al-R wherein R is selected from the group consisting of chloro, -O-R" wherein R" is selected from the group consisting of methyl, ethyl, isopropyl and tertiary butyl and OSO R wherein R is selected from the group consisting of alkyl having l4 carbon atoms, phenyl, p-chlorophenyl, hydroxyphenyl, tolyl and 2-oxo-l0-bornanyl, and

Z represents a member selected from the group consisting of C R2 CH wherein R is selected from the group consisting of a. COR wherein R is selected from the group consisting of (i) methyl, (ii) ethyl, in which cases R is methyl, (iii) phenyl, in which case R is selected from the group consisting of methyl, acetyl and COOR wherein R is alkyl containing l4 carbon atoms,

b. COOR., wherein R, has the meaning given above in which case R represents a member selected from the group consisting of methyl, C=N and COOR., wherein R, has the meaning given above,

c. NO in which case R represents a member selected from the group consisting of bromine and alkyl containing 1-3 carbon atoms; and

wherein R represents a member. selected from the group consisting of d. methyl, in which case R is COOR and R represents O-R wherein R represents alkyl having l4 carbon atoms, and e. hydrogen, in which case R is selected from the group consisting of iv. COR wherein R is selected from the group consisting of methyl, in which case R is selected from the group consisting of methyl and phenyl, and phenyl, in which case R is methyl, v. COOR in which case R is selected from the group consisting of methyl, phenyl and O-R,, wherein R has the meaning given above; and vi. -C N in which case R represents O-R wherein R has the meaning given above.

8. The antiperspirant cosmetic aerosol composition of claim 7 wherein said active compound is present in an amount between l5 percent by weight of said composition.

9. The antiperspirant cosmetic aerosol composition of claim 7 which also contains a lower alkanol selected from the group consisting of ethanol and isopropanol.

UNITED STATES PATENT OFFICE Page 1 of 2 CERTIFICATE OF CORRECTION Patent: No. 3I929r986 Dated December 30, 1975 lnventofls) Claude Bouillon, Pierre Dufaure and Georges Rosenbaum It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In the Heading:

Under [62] Pat. No. 3,819,761 should read Column 1, line 6,- should read --U.S. Pat. No. 3,8l9,67l-.

Column 3, line 5, the structural formula should read c -H 0c 0- 2 5 X AlCl NEC 0 Column 9, in Scheme A, the structural formula immediately above (4) should read UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No; 3,929,986 Dated December 30, 1975 In'venwfls) Claude Bouillon et al. Page 2 of 2 It is certified that error appears in the above-identified patent I and that said Letters Patent are hereby corrected as shown below:

Column 11, in Scheme B, the structural formula immediately above (7 should read Column 12, in Scheme B, the structural formula immediately above (8) should read s /c o R -c Al-Cl \CHZ-Q/ Signed and Scaled this.

Thirtieth Day of November 1976 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner of'Parenls and Trademarks 

1. AN ANTIPERSPIRANT COSMETIC COMPOSITION COMPRISING IN A SOLVENT SELECTED FROM THE GROUP CONSISTING OF WATER, A LOWER ALKANOL AND AN AQUEOUS SOLUTION OF SAID LOWER ALKANOL, 0.2-30 PERCENT BY WEIGHT OF AN ACTIVE COMPOUND HAVING THE FORMULA
 2. The composition of claim 1 wherein said active compound is selected from the group consisting of 2-chloro-5,5-bis-(ethoxycarbonyl)-1,3,2-dioxaluminane, 2-chloro-5-cyano-5-ethoxycarbonyl-1,3,2-dioxaluminane, 2-chloro-5-bromo-5-nitro-1,3,2-dioxaluminane, 2-chloro-5-ethoxycarbonyl-4-ethoxy-1,3,2-dioxaluminin, 2-chloro-5-ethoxycarbonyl-4-methyl-1,3,2-dioxaluminin, 2-chloro-5-acetyl-4-methyl-1,3,2,-dioxaluminin, 2-methanesulfonyloxy-5,5-bis-(ethoxycarbonyl)-1, 3, 2-dioxaluminane, 5,5-bis-(ethoxycarbonyl)-2-p-toluene sulfonyloxy-1,3,2-dioxaluminane, 5-acetyl-2-chloro-5-methyl-1,3,2-dioxaluminane, 5-benzoyl-2-chloro-5-methyl-1,3,2-dioxaluminane, 2-chloro-5-cyano-4-ethoxy-1,3,2-dioxaluminane, 5-benzoyl-2-chloro-5-ethoxycarbonyl-1,3,2-dioxaluminane, 2-chloro-5-ethoxycarbonyl-5-methyl-1,3,2-dioxaluminane, 2-chloro-5-ethoxycarbonyl-4-phenyl-1,3,2-dioxaluminane, 5-acetyl-5-benzoyl-2-chloro-1,3,2-dioxaluminane, 5-acetyl-2-chloro-4-phenyl-1,3,2-dioxaluminin, 5-benzoyl-2-chloro-4-methyl-1,3,2-dioxaluminin and 2-chloro-4-ethoxy-5-ethoxycarbonyl-6-methyl-1,3,2-dioxaluminin.
 3. The composition of claim 1 wherein said active compound is present in amounts between 0.5-25 percent by weight of said composition.
 4. An antiperspirant cosmetic powder composition comprising in a carrier selected from the group consisting of talc, magnesium carbonate, rice starch, corn starch, kaolin, bentonite, lithium stearate, zinc stearate, magnesium stearate and mixtures thereof, 0.2-30 percent by weight of an active compound having the formula
 5. The antiperspirant cosmetic powder composition of claim 4 wherein said active compound is present in an amount between 5-25 percent by weight of said composition.
 6. The antiperspirant cosmetic powder composition of claim 4 which also contains a liquified aerosol propellant selected from the group consisting of trichlorofluoromethane, dichlorodifluoromethane and mixtures thereof, said composition being packaged under pressure in an aerosol container.
 7. An antiperspirant cosmetic aerosol composition packaged under pressure in an aerosol container comprising in a liquified aerosol propellant selected from the group consisting of trichlorofluoromethane, dichlorodifluoromethane and mixtures thereof, 0.2-30 percent by weight of an active compound of the formula
 8. The antiperspirant cosmetic aerosol composition of claim 7 wherein said active compound is present in an amount between 1-5 percent by weight of said composition.
 9. The antiperspirant cosmetic aerosol composition of claim 7 which also contains a lower alkanol selected from the group consisting of ethanol and isopropanol. 